Herein a convenient synthetic method to obtain 2,2,3,3-tetrasilyltetrasilane 3 and 2,2,3,3,4,4-hexasilylpentasilane 4 on a multigram scale is presented. Proton-coupled Si NMR spectroscopy and single-crystal X-ray crystallography enabled unequivocal structural assignment. Owing to their unique properties, which are reflected in their nonpyrophoric character on contact with air and their enhanced light absorption above 250 nm, 3 and 4 are valuable precursors for liquid-phase deposition (LPD) and the processing of thin silicon films. Amorphous silicon (a-Si:H) films of excellent quality were deposited starting from 3 and characterized by conductivity measurements, ellipsometry, optical microscopy, and Raman spectroscopy.

In this contribution, a convenient synthetic method to obtain tris(trimethoxysilyl)silanides (M=Li, Na, K, Cu) 5 a–d is described. 5 a–d are easily accessible deriving from dodecamethoxyneopantasilane 4 in excellent yields and could be fully characterized via NMR spectroscopy and X‐ray crystallography. The efficiency of 5 a–d to serve as a new building block in silicon chemistry is demonstrated by the reactions with two different types of electrophiles (carbon‐ and silicon‐electrophiles). In all cases the salt metathesis reaction gave rise to novel polysilanes in excellent yields. The possibility of a post‐functionalization to perhydropolysilanes as well as perchloropolysilanes enables the synthesis of new precursors for silicon deposition.

A solvent-free procedure for forming amide bonds without exclusion of air and moisture is described. Using tetramethoxysilane 1, hexamethoxydisilane 2 and dodecamethoxy-neopentasilane 3 as coupling agent carboxylic acids and amines...

Herein a convenient synthetic method to obtain 2,2,3,3‐tetrasilyltetrasilane 3 and 2,2,3,3,4,4‐hexasilylpentasilane 4 on a multigram scale is presented. Proton‐coupled 29Si NMR spectroscopy and single‐crystal X‐ray crystallography enabled unequivocal structural assignment. Owing to their unique properties, which are reflected in their nonpyrophoric character on contact with air and their enhanced light absorption above 250 nm, 3 and 4 are valuable precursors for liquid‐phase deposition (LPD) and the processing of thin silicon films. Amorphous silicon (a‐Si:H) films of excellent quality were deposited starting from 3 and characterized by conductivity measurements, ellipsometry, optical microscopy, and Raman spectroscopy.

New methoxylated oligosilyl-substituted metallocenes were synthesized by the reaction of two oligosilanides with different metallocene dichlorides (M = Ti, Zr, and Hf). The first investigated tris(trimethoxysilyl)silanide [(MeO) 3 Si] 3 SiK ( 1 ) underwent a selective monosubstitution to the respective oligosilyl-decorated metallocenes [(MeO) 3 Si] 3 SiMClCp 2 ( 2 – 4 ). Surprisingly, the attempted disilylation with this silanide was not possible. However, in the case of titanocene dichloride, a stable radical [(MeO) 3 Si] 3 SiTiCp 2 ( 5 ) was formed. The unsuccessful isolation of bisilylated metallocenes encouraged us to investigate the reactivity of another silanide. Therefore, we synthesized a hitherto unknown disilanide K[(MeO) 3 Si] 2 Si(SiMe 2 ) 2 Si[(MeO) 3 Si] 2 K ( 8 ), which was accessible in good yields. The reaction of compound 8 and different metallocene dichlorides (M = Ti, Zr, and Hf) gave rise to the formation of heterocyclic compounds 9 – 11 in good yields.